JPS5917743B2 - Method for producing mixed complex salt of methine dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the following formula 1: [wherein M represents zinc, cadmium, lead or manganese, M2 represents cobalt, copper or nickel,
R represents a cyano group, methyl group, phenyl group, methoxycarbonyl group or benzoxazolyl group, Z1 represents an oxygen or sulfur atom or an imino group, X1 and Y1 are hydrogen or a halogen atom, or have 1 to 6 carbon atoms. represents an alkyl group, x represents a hydrogen atom,
Y represents a halogen atom or a methoxycarbonyl group, z represents an aryloxy group which may be substituted with a halogen atom, m represents O to 4, n represents O to 4, and p represents 0 to 3. Representation, and m+
The sum of n+p must be 4, and M1:M2
The atomic ratio of is between 5:95 and 95:5.

This invention relates to a method for producing a mixed complex salt of a methine dye represented by the following. In the above definitions, the term aryl represents, for example, a naphthyl group, but preferably a phenyl group which may be substituted with a halogen atom.

Homogeneous metal complexes of 3-benzimidazolyl-methylene-isoindolinone are described in DE-A-2359791.

The cobalt complexes mentioned therein are distinguished by remarkable light and weathering resistance, but they give plastics and varnishes a reddish-yellow coloring with some opacity. Zinc complexes, on the other hand, give a shiny green-yellow tint, but they are inferior to cobalt complexes in light and weathering resistance. The light resistance and weathering resistance of the M1 complex salt are synergistically improved by forming a mixed complex salt with the M2 complex salt.

The practical use of M, complex salts which are otherwise shiny and productive but not lightfast becomes more important thereby. Preferred mixed complex salts are those of the formula 1, in which R represents a cyano group and Z1 represents an imino group, and especially those of the formula: (wherein Ml.M2, X1 and Y1 are defined above) It is the same as what was done.

) is a complex salt represented by γ. Particularly preferred mixed complex salts have the formulas given above (wherein X1 and Y1 represent hydrogen atoms and the atomic ratios of M1:M2 are 10, 90 and 9
between 0 and 10, and M1 represents zinc and M2 represents cobalt. ) is a complex salt represented by The mixed complex salt according to the invention has the following formula: ノ(R)X)Y)z)x1)Y1)z1)m) n and p are as defined before.

) isointrinon represented by 5 to 95 mol% of zinc, cadmium, lead or manganese salt and cobalt,
It is obtained by metallization with a mixture consisting of 95 to 5 mol % of copper or nickel salts. The isointrinones used as starting materials are known compounds.

They are the azoles represented by the following formula: In particular, the azoles represented by the following formula: [In the above three formulas, R. Xl, Y1, Z1, X. Y. Z, M
．． n and p are as defined above, and V is of the formula: ]C or ha, where X3 represents an imino or thio group and
3 represents a halogen atom, lower alkoxy or a secondary amino group.

) represents a group represented by ] is obtained by condensation with isointrinone. As azoles, mention may be made of oxazoles, thiazoles or especially imidazoles.

For example: 2-cyanomethyl-benzimidazole 2-cyanomethyl-4-chloro-benzimidazole 2
-cyanomethyl-5-chloro-benzimidazole 2-
Cyanomethyl-5,6-dichloro-benzimidazole 2-cyanomethyl-4-chloro-6-methyl-benzimidazole Penzimidazoli-2-ylmethyl acetate 2-cyanomethyl-benzthiazole 2-cyanomethyl-5-chlorobenzthiazole Nore 2
-cyanomethyl-6-chloro-benzthiazole 2-cyanomethyl-J[chlorobenzthiazole 2-cyanomethyl-5-methyl-benzthiazole 2-cyanomethyl-6-methyl-benzthiazole 2-ethyl-
Benzimidazole 2-benzyl-benzimidazole 2-ethyl-benzthiazole 2-benzyl-benzthiazole 2-ethyl-benzoxazole 2-benzyl-benzoxazole 2-cyanomethyl-benzoxazole bis-(2-benzoxazolyl)-methane Possible isointrinones are preferably 3-iminoisointrione or 3,3-dimethoxyisointrinon or 3.
It is an alkali salt of 3-dimethoxyisointrinon.

For example, the following is cited: 3,3-dimethoxy-4
・5,6,7-tetrachloroisoindolinone-13
-Imino-5,6-dichloroisoindolinone-13
・3,6-trimethoxy-4,5,7-trichloroisoindolinone-13-imino-4,5,7-trichloro-6-phenoxyisoindolinone-113,3,6
-trimethoxy-4,5,7-tripromoisoindolinone -13,3,4,6-tetramethoxy-5,7-dichloroisoindolinone -13-iminoisoindolinone (imino-phthalimide)3. 3-dimethoxy-4,6-dichloroisoindolinone-13,3-dimethoxy-4,5,6,7-tetrapromoisoindolinone-13,3-dimethoxy-5,7-dichloro-4
・6-diphenoxyisoindolinone-13,3-dimethoxy-4,5,7-trichloro-6-(4'-chlorophenoxy)-isointrinon-13-imino-4
・5.6.7-tetrachloroisoindolinone-13.
3-dimethoxy-4,7-dichloroisoindolinone 13,3-dimethoxy-4-chloroisoindolinone 13,3-dimethoxy-6-iodoisoindolinone 1 Formate of the above cited metal, Acetate or stearate are preferably used for the metallization.

It is advantageous to carry out the process at elevated temperatures in an organic solvent, such as an alcohol, such as methanol, ethanol, isopropanol, glacial acetic acid or preferably ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether or dimethylformamide.

It is also possible to use mixtures of the abovementioned solvents or water. The colorants according to the invention are suitable for use in high molecular weight organic substances, such as cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate, cellulose butyrate, natural or synthetic resins, such as polymerized or condensed resins, such as aminoplasts, especially urea/ Formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and Silicone resins are useful pigments used in finely divided form to color silicone resins, alone or in mixtures.

It is immaterial whether the high molecular weight compounds are in the form of plastics, melts or spinning solutions, varnishes, paints or printing inks.

Depending on their intended use, it is advantageous to use the pigments according to the invention as toners or in the form of formulations. It is often advantageous to mill the pigment to bring it into a finely divided state. In the following example, parts and %
is expressed by weight unless otherwise stated.

Example 1 The following formula: Obtained by condensing limide hydrochloride with 2-cyanomethylbenzimidazole in ethylene glycol monoethyl ether.

In place of the 4 parts of 4A above, use the respective amounts of zinc acetate dihydrate listed in the columns of Table 1 and in place of the 0.524 parts above, use the respective amounts of cobalt acetate tetrahydrate in the columns, and Carrying out a similar process, it has the atomic proportions of zinc to cobalt (%) as described in the columns and has better light and weathering resistance than the mixtures obtained from pure complex salts with the same metal proportions. A pigment is obtained. Example 10j If an equivalent of cadmium acetate, lead or manganese is used in place of zinc acetate in Examples 1 to 9, and an equivalent of copper acetate or nickel is used in place of cobalt acetate, the same ratio of pure Mixed complex salts of the same color are produced which all have better lightfastness and weathering resistance than those obtained by mixing the same complex salts together.

Example 11 11.44 parts of the dye of Example 1 were mixed with 100 parts of water and 5 parts of sodium hydroxide solution (30%).

32 parts and wetting agent [TamOl NNOK-
Stir in 0.5 part of SA at 90°C for 2 hours.

Next, a solution of 3.940 parts of zinc acetate dihydrate and 0.498 parts of cobalt acetate tetrahydrate in 50 parts of water is added, and the temperature is maintained at about 95°C for 6 to 15 hours with stirring. . The batch is hot filtered and the filter cake is thoroughly washed with hot water, then with methanol and again with water and dried at about 100° C. under reduced pressure to form the mixed complex salt corresponding to that obtained in Example 1. generate. By the same method but using other zinc acetate/cobalt acetate ratios, mixed complex salts with corresponding zinc-cobalt contents are obtained.

Examples 12-52 In place of the dye of Example 1, the dye of column 1 of Table 2 is used, and the metal in the column is added according to Example 1 or 11 in the % atomic proportions indicated in the column. Metallization with a mixture of salts and metal salts in the columns gives mixed complex salt pigments with the shades indicated in the columns.

The light and weathering resistance of the mixed complex salts is better than that of mixtures obtained from pure amphoteric salts with the same metal proportions.

Reference example 1 Stabilized polyvinyl chloride 65 parts, dioctyl phthalate 35 parts
1 part and 0.2 part of the pigment obtained according to Example 1 are stirred together and rolled in a two-roll mill at 140 DEG C. for 7 minutes.

A glossy yellow sheet is obtained which has very good fastness to light and migration. Reference Example 2 Titanium dioxide 10y and pigment 27 produced in Example 1
in a ball mill with 887 g of a mixture consisting of 26.47 g of coconut alkyd resin, 247 g of melamine/formaldehyde resin (50% solids content), 5.8 g of ethylene glycol monomethyl ether and 28.87 g of xylene.
Mill for 8 hours.

The resulting varnish was sprayed onto an aluminum plate and heated at room temperature for 3
Pre-drying for 0 minutes and stopping for 30 minutes at 120° C. gives a glossy yellow finish with good dyeing strength, characterized by overstripe, free zinc, very good fastness to light and weathering. Reference Example 3 (Acrylic Resin Stopping Enamel) 4 parts of the finely divided pigment of Example 1 are stirred in 20 parts of a solvent consisting of the following composition: parts.

After a complete dispersion is obtained (approximately 15 minutes depending on the nature of the stirrer)
~60 minutes), the following binder: Baycryl
rylL) 530 (acrylic resin (51% in xylene/butanol 3:1) 48.3 parts and maprenal (M
23.7 parts of TTX (melamine resin) (55% in butanol) are added.

After short homogenization, the varnish is applied in the usual manner, for example by spraying or dipping or coil coating, to form a continuous coating of the metal plate and stoping (13
(at 0°C for 30 minutes).

The yellow finish obtained is characterized by very good leveling properties, high gloss and excellent fine distribution of the pigments, as well as good weathering resistance. Reference Example 4 Non-matte polyethylene terephthalate particles suitable for fiber production and 1% of the dye of Example 1 are vibrated together in a sealed container on a vibrator for 15 minutes.

Uniformly colored granular particles were spun into a melt spinning machine (285℃±3
℃, holding time in the spinner approximately 5 minutes) into filaments. The filament is pulled on a tension thread machine and wound into a tube. Outstanding light fastness, excellent fastness to washing, dry cleaning, cross-dye inking and sublimation, as well as very good fastness to chlorite bleaching and very good resistance to abrasion after heat curing of the colored substances mentioned above. A glossy yellow coloration with good wax fastness is obtained. Reference Example 5 Polypropylene particles suitable for fiber production are colored using 1% of the dye of Example 1, extruded and spun as described in Reference Example 4 to give a yellow color with pronounced waxiness. Fiber is obtained.

Claims (1)

[Claims] Primary formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, M_1 represents zinc, cadmium, lead or manganese, M_2 represents cobalt, copper or nickel, R represents a cyano group, methyl group, phenyl group, methoxycarbonyl group or benzoxazolyl group, Z_1 represents an oxygen or sulfur atom or an imino group, X_1 and Y_1 are hydrogen or halogen atoms, and have 1 to 6 carbon atoms. represents an alkyl group, X represents a hydrogen atom, Y represents a halogen atom or a methoxycarbonyl group, Z represents an aryloxy group which may be substituted with a halogen atom, m represents 0 to 4, and n represents 0 to 4, p represents 0 to 3, and the sum of m+n+p must be 4, and M_1:
The atomic ratio of M_2 is between 5:95 and 95:5. ] In the method for producing a mixed complex salt of methine dye represented by the following formula II: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II]
(wherein X_1, Y_1, Z_1, R, Xm, Yn and Zp have the meanings given in the following formula I) isoindolinone represented by A method for producing a mixed complex salt of a methine dye represented by the above formula I, which comprises metallizing with a mixture consisting of 95 to 5 mol % of a salt of cobalt, copper or nickel.